US3546244A - Thiocyanoindole derivatives - Google Patents

Thiocyanoindole derivatives Download PDF

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Publication number
US3546244A
US3546244A US695352A US3546244DA US3546244A US 3546244 A US3546244 A US 3546244A US 695352 A US695352 A US 695352A US 3546244D A US3546244D A US 3546244DA US 3546244 A US3546244 A US 3546244A
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US
United States
Prior art keywords
thiocyanoindole
compositions
methanol
compound
fungi
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US695352A
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English (en)
Inventor
Stig Hjalmar Johanne Akerstrom
Albert Tempel
Bengt Hjalmar Gullfeldt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
US Philips Corp
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US Philips Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from SE00193/67A external-priority patent/SE347422B/xx
Application filed by US Philips Corp filed Critical US Philips Corp
Application granted granted Critical
Publication of US3546244A publication Critical patent/US3546244A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring

Definitions

  • the present invention relates to compounds represented by the general Formula I in which formula R stands for a hydrogen atom or anyone of the radicals alkyl, aryl, aralkyl and acyl R stands for a hydrogen atom or anyone of the radicals alkyl, alkoxy, alkylthio, aralkyl, aryl, carboxyl and trifiuoromethyl,
  • R R may be the same or different and represent a hydrogenor halogenatom or anyone of the radicals alkyl, acyloxy, alkoxy, alkylthio, hydroxy, cyanogen, thiocyanogen, nitro and nitro-fluoromethyl.
  • the compounds of the general Formula I influence the growth of microbiological organisms.
  • the compounds are suitable to be used in compositions for the control of plant pathogenical micro-organisms which occur as pests in both forests and on agricultural plants.
  • the compounds of the invention have also proved to be extremely useful in compositions for the control of certain fungi and bacteria which cause trouble in connection with the preservation of particulrly forestry products such as wood, pulp and paper, but also paints.
  • the compounds of the invention can advantageously be used in compositions for control of the formation of slime, e.g., in the forest industry.
  • compositions for the control of microbiological organisms which is characterized by a content of at least one of the compounds of the general Formula I.
  • Said composition can be prepared in the usual way by mixing the active compound with a solid or liquid inert diluent if desirable together with surface-active agents, such as emulsifiers and wetting agents, and/or dispersing agents.
  • surface-active agents such as emulsifiers and wetting agents, and/or dispersing agents.
  • the compositions according to the invention possess an essential lower degree of toxicity than the known compositions containing mercury and do not show the drawbacks mentioned above.
  • compositions according to the present invention have proved to have at least as wide a spectrum, in regard to both fungi and bacteria, as the previously used compositions containing mercury, and it has also proved that they can often be used in lower concentrations.
  • R represents an alkyl group
  • a group contains from 1-10 carbon atoms, so as for exam ple a methyl-, propyl-, or heptyl group.
  • R or R represents an aryl or aralkyl group
  • such a group comprises form 62O carbon atoms so as for example a phenyl group, naphthyl group, benzyl group or trityl group.
  • R represents an acyl group
  • this group preferably contains from 2-12 carbon atoms, for example a benzoyl group, naphthoyl group, or acetyl group.
  • R R R R or R7 represents an alkyl, alkylthio or alkoxy group, such a group generally comprises from 1-7 carbon atoms, for example, a methyl-, ethyl-, heptyl-, methoxy-, ethoxy-, methylthio-, or ethylthio group.
  • the compounds of the invention are new with the exception of 3-thiocyanoindole and can be prepared according to methods known for the preparation of such compounds or, according to methods analogous thereto.
  • inventive compounds may be prepared.
  • R stands for a hydrogen atom or anyone of the radicals alkyl, alkoxy, alkylthio, aralkyl, aryl, carboxyl and trifluoromethyl,
  • R R may be the same or different and represent a hydrogen-or halogenatom or anyone of the radicals alkyl, acyloxy, alkoxy, alkylthio, hydroxy, cyanogen,
  • EXAMPLE 1 l-methyl-3-thiocyanoindole 60 g. of potassium thiocyanate and 150 ml. of methanol was charged in a 500 ml. flask, and cooled with Dry Iceacetone, while stirring, to '55 to -60 C., after which a cooled solution of 13.5 g. of bromine in 150 ml. of methan01 was dripped in during a time of 40 minutes at '55 C. the same way, a solution of 30 g. of l-methylindole in 125 ml. of methanol was added. After stirring for a further 4 hours, at which the temperature was allowed to rise to 20 C., the mixture was poured out on 400 g. of ice+water. As soon as the ice had melted, the precipitation was filtered off, washed with Water, dried and recrystallized from benzene-ligroin. Melting point 87-89" C.
  • EXAMPLE 2 1-acetyl-3-thiocyanoindole 10 g. of S-thiocyanoindole and 125 ml. of acetic anhydride was charged into a 250 ml. flask which was provided with stirrer and refluxer. After heating with refluxing for 9 hours, followed by cooling to room temperature, the flask was placed in a refrigerator for crystallization. The crystals were filtered off and re-crystallized from benzene-ligroin. Melting point 120 C.
  • the toxicity of the composition has been tested, and then applied perorally on rats, and it has then been found that the value for a lethal dose with 50% lethality (LD 50) is 160:60 mg./kg. This value can be regarded as entirely safe when using the quantities (100-1000 p.p.m.; p.p.m.:parts per million) used in the present case.
  • a test series was carried out with compositions according to the present invention for the purpose of controlling certain fungi proved to involve considerable difiiculties when cultivating pine and fir plants, particularly in forest nurseries.
  • the problem of protecting pine and fir plants in forest nurseries is very great, among other things, owing to the fact that the material is comparatively expensive, as it often takes a rather long time to obtain suitable specimens of plants.
  • the problem has become still more complicated in as much as plastic greenhouses are now used to a great extent when rising fir and pine plants and, consequently the fungi that cause damages have better possibilities of developing than previously.
  • the fungi which primarily come into question and with which tests have been made are as follows: Rhizia inflata, Fomes annosus, Crumenula abietina, Fusarium culmorum, Fusarium avenaciwm, Botrytis cinerea, Trichoderma: viride and Herpotrichia nigro.
  • Rhizia inflata Fomes annosus
  • Crumenula abietina Fusarium culmorum
  • Fusarium avenaciwm Fusarium culmorum
  • Botrytis cinerea Trichoderma: viride
  • Herpotrichia nigro Herpotrichia nigro.
  • compositions used are those containing zinc carbamate, 1-phenylthiosemicarbamide and dichlorotetrafiuoroacetone and at the trials made, the results obtained with the compositions according to the present invention were compared just with those obtained with the known compositions mentioned above.
  • compositions according to the invention so as for instance compositions containing 3- thiocyano-indole, N-heptyl-thiocyanoindole or N-methylthiocyanoindole gave a very good pesticidal effect and this effect was considerably higher than what had been obtained with the known compositions.
  • compositions according to the present invention have proved to have a considerably better effect that the other compositions tested.
  • compositions according to the present invention give a considerably better effect than the known compositions.
  • a number of fungi that cause damages on lumber were tested in a fourth test series.
  • the fungi in question were: Scopularia phycomyces, Pullularia pullulans, Coniophora souna, Merulius lacrymans, Lentinus lepz'deus Poria vaporaria, Polyporus versicolor, Ceratocystio philifora.
  • the tests were carried out in the same way as at the last of the foregoing test series, and the same compositions were used. It can be established from the test results that also as regards these 8 fungi, which cause much trouble at the preservation of lumber, the composition according to the present invention had an effect which is considerably superior to that of the other three compositions tested.
  • MIC minimum inhibiting concentration
  • compositions according to the present invention can be available in different forms including dry powders, Wettable powders, emulsifying liquids, dispersions, emulsions, fumigating compounds and aerosols.
  • These wellknown formulations can be prepared in the usual way by mixing the active ingredient with a solid or liquid inert carrier if desired in combination with surface-active agents such as wetting-agents and emulsifiers, dispersing agents and adhesives.
  • EXAMPLE 1 Dry powder In a ball mill or other mixing device, a mixture of 10 weight parts of 3-thiocyanoindole, weight parts of talcum and weight parts of plaster of Paris are mixed.
  • EXAMPLE 2 Dry powder A through mix was prepared by mixing 5 parts of weight of 3-thiocyanoindole and 95 parts of weights of china clay, whereafter the mixture was ground in a mill.
  • EXAMPLE 3 Wettable powder 20 weight parts of 3-thiocyanoindole are fine-ground together with weight parts of kaolin, 5 weight parts of lignin sulphamate and 3 weight parts of fat-alcohol sulphate.
  • the Wettable powder thus obtained forms by diluation with water a stable watery dispersion of the active compound.
  • Wettable powder Wettable powders were prepared by grinding the following mixture (parts of weight in a mill):
  • Tucen 60 (a dispersing agent in a polyoxyethylene derivation of sorbitanemonosteant) 2 Ethylon CP /2 China clay, ad
  • Emulsifying liquid For the preparation of compositions suitable to be diluted with water in order to form a stable emulsion, the following components were mixed:
  • EXAMPLE 7 Emulsifying liquid In room temperature or low heat, 10 weight parts of 3-thiocyanoindole, 50 weight parts of xylene, 10 weight parts of diethylene-glycol-diethyl ether and 8 weight parts of nonylphenol polyglycol ether, are mixed, giving a solution which can be emulsified in water.
  • R is a member selected from the group consisting of hydrogen, alkyl of 1-10 carbon atoms, phenyl, naphthyl, benzyl and trityl
  • R is a member selected from the group consisting of hydrogen, phenyl, naphthyl, benzyl, trityl, alkyl of 1-7 carbon atoms, alkylthio of l-7 carbon atoms, alkoxy of l-7 carbon atoms and trifluoromethyl
  • R R R and R are each members selected from the group consisting of hydrogen, halogen, hydroxy, cyano, thiocyano, nitro, nitrofluoromethyl, alkyl of 1-7 carbon atoms, alkoxy of 1-7 carbon atoms and alkylthio of 1-7 carbon atoms With the proviso that at least one of R R R and R is other than hydrogen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Indole Compounds (AREA)
  • Closures For Containers (AREA)
US695352A 1967-01-04 1968-01-03 Thiocyanoindole derivatives Expired - Lifetime US3546244A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE00193/67A SE347422B (cs) 1967-01-04 1967-01-04
SE772267 1967-06-02

Publications (1)

Publication Number Publication Date
US3546244A true US3546244A (en) 1970-12-08

Family

ID=26654127

Family Applications (2)

Application Number Title Priority Date Filing Date
US695352A Expired - Lifetime US3546244A (en) 1967-01-04 1968-01-03 Thiocyanoindole derivatives
US44602A Expired - Lifetime US3646210A (en) 1967-01-04 1970-06-08 Fungicidal and bactericidal composition and method containing 3-thiocyanoindole derivatives

Family Applications After (1)

Application Number Title Priority Date Filing Date
US44602A Expired - Lifetime US3646210A (en) 1967-01-04 1970-06-08 Fungicidal and bactericidal composition and method containing 3-thiocyanoindole derivatives

Country Status (5)

Country Link
US (2) US3546244A (cs)
DE (1) DE1695579A1 (cs)
FI (1) FI50036C (cs)
GB (1) GB1215631A (cs)
NO (1) NO125758B (cs)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925304A (en) * 1972-11-20 1975-12-09 Tenneco Chem Surface-coating compositions containing n-(indazolyl-n' 1'-methyl)dialkanolamines
DE3533856A1 (de) * 1985-09-23 1987-05-21 Wilhelm Koenig Vorrichtung zur herstellung von hartdisketten aus glas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
FI50036C (fi) 1975-12-10
US3646210A (en) 1972-02-29
GB1215631A (en) 1970-12-16
NO125758B (cs) 1972-10-30
FI50036B (cs) 1975-09-01
DE1695579A1 (de) 1971-04-22

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